EP3309873A1 - Anode active material for lithium secondary battery, preparation method therefor, and lithium secondary battery containing same - Google Patents
Anode active material for lithium secondary battery, preparation method therefor, and lithium secondary battery containing same Download PDFInfo
- Publication number
- EP3309873A1 EP3309873A1 EP16811925.3A EP16811925A EP3309873A1 EP 3309873 A1 EP3309873 A1 EP 3309873A1 EP 16811925 A EP16811925 A EP 16811925A EP 3309873 A1 EP3309873 A1 EP 3309873A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- coating layer
- carbon
- silicon
- active material
- anode active
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/02—Silicon
- C01B33/021—Preparation
- C01B33/027—Preparation by decomposition or reduction of gaseous or vaporised silicon compounds other than silica or silica-containing material
- C01B33/029—Preparation by decomposition or reduction of gaseous or vaporised silicon compounds other than silica or silica-containing material by decomposition of monosilane
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/364—Composites as mixtures
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/386—Silicon or alloys based on silicon
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Definitions
- the present disclosure relates to an anode active material for a lithium secondary battery, a preparation method thereof, and a lithium secondary battery including the anode active material.
- a lithium secondary battery which is charged and discharged through oxidation/reduction of lithium ions, includes a cathode, an anode, an ion exchange membrane between the cathode and the anode, and an electrolyte.
- a conventional carbonaceous anode active material has merely a theoretical capacity of about 372 mAh/g, and significantly reduced output characteristics, particularly in a high-rate charging condition, due to a mechanism of intercalation and deintercalation of lithium ions in a carbon interlayer during charging and discharging.
- An alloy-based material that is currently under research also has fairly low electrical conductivity and may undergo considerable volume expansions during charging and discharging, leading to severe damage of electrode plates and a sharp reduction in capacity. Therefore, there are difficulties in commercializing the alloy-based material.
- the present invention provides an anode active material for a lithium secondary battery, having greater capacity than conventional commercialized carbonaceous anode active materials and improved lifetime and output characteristics, and a method of preparing the anode active material.
- an anode active material for a lithium secondary battery includes: carbon particles having a spherical shape; a first carbon coating layer present on surfaces of the carbon particles; a silicon coating layer present on the first carbon coating layer and including silicon nanoparticles; and a second carbon coating layer present on the silicon coating layer.
- the carbon particles having the first carbon coating layer thereon may have an 10% or greater increased Brunauer-Emmett-Teller (BET) specific surface area with respect to a BET specific surface area of the carbon particles having the spherical shape.
- BET Brunauer-Emmett-Teller
- the carbon particles having the first carbon coating layer thereon may have an 10% or greater reduced Brunauer-Emmett-Teller (BET) specific surface area with respect to a BET specific surface area of the carbon particles having the spherical shape.
- BET Brunauer-Emmett-Teller
- the silicon nanoparticles may be semicrystalline.
- the first carbon coating layer may partially include a mixed layer of silicon and carbon.
- the mixed layer of silicon and carbon may have a concentration gradient in which an amount of silicon decreases in the direction of a core.
- the silicon coating layer present on the first carbon coating layer may be in a mixed form of a film and an island.
- a content ratio of silicon to carbon may be about 3:97 to about 20:80, with respect to a total weight of the anode active material.
- the anode active material may include 2wt% to 6wt% of the first carbon coating layer, 4wt% to 20wt% of the silicon coating layer, and 1.5wt% to 10wt% of the second carbon coating layer, each based on a total of 100wt% of the anode active material, and the remainder may be the carbon particles.
- the carbon particles may include graphite, amorphous carbon, or a combination thereof.
- the carbon particles may have a particle diameter of 5 ⁇ m to 20 ⁇ m.
- the first carbon coating layer may have a thickness of 5 nm to 200 nm.
- the silicon coating layer may have a thickness of 20 nm to 60 nm.
- the second carbon coating layer may have a thickness of 5 nm to 200 nm.
- a method of preparing an anode active material for a lithium secondary battery includes: preparing carbon particles having a spherical shape; forming a first carbon coating layer on surfaces of the carbon particles; forming, on the first carbon coating layer, a silicon coating layer including silicon nanoparticles; and forming a second carbon coating layer on the silicon coating layer.
- the forming of the first carbon coating layer on the surfaces of the carbon particles may be performed using a sol-gel method.
- the forming of the first carbon coating layer on the surfaces of the carbon particles may be performed using a chemical vapor deposition method.
- the silicon nanoparticles may be amorphous.
- the silicon coating layer may be deposited in a mixed form of a film and an island.
- a silicon-based precursor for example, silane (SiH 4 ), dichlorosilane (SiH 2 Cl 2 ), silicon tetrafluoride (SiF 4 ), silicon tetrachloride (SiCl 4 ), methylsilane (CH 3 SiH 3 ), disilane (Si 2 H 6 ), or a combination thereof may be used.
- the forming of the second carbon coating layer on the silicon coating layer may be performed using a physical milling method, a sol-gel method, or a chemical vapor deposition method.
- a carbon precursor selected from the group consisting of a rayon-based carbon precursor, a PAN-based carbon precursor, a pitch-based carbon precursor, and a combination thereof may be used.
- a lithium secondary battery includes: a cathode; an anode; and an electrolyte, wherein the anode include the anode active material according to any of the embodiments.
- an anode active material for a lithium secondary battery having improved lifetime characteristics and output characteristics, and a method of preparing the anode active material may be obtained.
- an anode active material for a lithium secondary battery including: carbon particles having a spherical shape; a first carbon coating layer present on surfaces of the carbon particles; a silicon coating layer present on the first carbon coating layer and including silicon nanoparticles; and a second carbon coating layer present on the silicon coating layer.
- the carbon particles having the first carbon coating layer thereon have an about 10% or greater increased or reduced Brunauer-Emmett-Teller (BET) specific surface area with respect to a BET specific surface area of the carbon particles not having the first carbon coating layer thereon.
- BET Brunauer-Emmett-Teller
- the anode active material may have a carbon/silicon composite structure.
- this carbon/silicon composite is formed from a blended slurry prepared using heterogeneous materials including a carbonaceous anode material and amorphous silicon powder, problems such as phase separation and dispersion may be resolved.
- the carbon/silicon composite may be implemented by depositing and/or coating silicon inside or over pores in the first carbon coating layer through chemical vapor deposition and then forming the second carbon coating layer thereon.
- a sol-gel method in forming the first carbon coating layer on the spherical carbon particles, may be used to obtain a structure having further increased Brunauer-Emmett-Teller (BET) specific surface area and porosity.
- BET Brunauer-Emmett-Teller
- a chemical vapor deposition method may be used to obtain a structure having further decreased BET specific surface area and porosity.
- the method of forming the first carbon coating layer may be appropriately selected according to desired characteristics of the anode active material.
- carbon particles may serve as a support layer for silicon particles that are to be deposited thereon, improving electrical conductivity and preventing inner sites of the spherical carbon particles from unnecessarily being coated with silicon, so as to mitigate volume expansion of a battery during charging and discharging.
- the carbon particles having the first carbon coating layer thereon may have, for example, a BET surface area of 2 m 2 /g to 50 m 2 /g, and in some embodiments, 2 m 2 /g to 7 m 2 /g, and in some other embodiments, 8 m 2 /g to 50 m 2 /g.
- a BET surface area of 2 m 2 /g to 50 m 2 /g and in some embodiments, 2 m 2 /g to 7 m 2 /g, and in some other embodiments, 8 m 2 /g to 50 m 2 /g.
- embodiments are not limited thereto, and the BET surface area of the carbon particles may be varied within these ranges.
- the carbon/silicon composite may be implemented to have a structure facilitating diffusion of lithium ions into the anode active material and at the same time providing high capacity.
- the second carbon coating layer as an outermost layer may provide electron transfer paths between or inside particles in manufacturing an electrode plate and thus to improve conductivity, and may control volume change of silicon during charging and discharging, thus improving stability of the electrode plate.
- the carbon/silicon composite as described above may have higher capacity, relative to a conventionally commercialized carbonaceous anode material, and improved lifetime and output characteristics.
- anode active material for a lithium secondary battery having the carbon/silicon composite structure as described above, will be described in greater detail.
- the silicon nanoparticles may be amorphous.
- the amorphous silicon nanoparticles may have a large capacity per weight of the particles, significantly reduced stress from volume expansion during charging (i.e., alloying with lithium), compared to crystalline silicon nanoparticles, and fast speeds of alloying and dealloying with lithium, which is advantageous in terms of charging and discharging rates.
- the silicon coating layer on the first carbon coating layer may be in a form of a film, an island, or a mixed form thereof.
- the silicon coating layer may be formed, by a chemical vapor deposition method, on the first carbon coating layer in a form of a film, an island, or a combination thereof, using an appropriate silicon-based precursor.
- the silicon coating layer when using the chemical vapor deposition method, may be formed in the form of an island at the beginning.
- the island form is an appropriate form to cope with volume expansion of the silicon nanoparticles included in the silicon coating layer.
- the silicon coating layer may be formed as a film and then finally as a mixed form of an island and a film at the end of the deposition. This may lead to an improved capacity per weight of the silicon particles and improved coulombic efficiency.
- the silicon nanoparticles may be simply adhered onto the first carbon coating layer by a strong physical force while source materials are mixed. In this case, it is nearly impossible to make the silicon nanoparticles adhere while uniformly controlling a degree of distribution. Furthermore, since the source materials are mixed and ground at the same time, the carbon material may be damaged, causing performance degradation when used in a battery.
- a content ratio of silicon to carbon may be 3:97 to 20:80, with respect to a total weight of the anode active material.
- the anode active material may exhibit a high capacity of 400 mAh/g to 800 mAh/g.
- the anode active material may include 2wt% to 6wt% of the first carbon coating layer, 4wt% to 20wt% of the silicon coating layer, 1.5wt% to 10wt% of the second carbon coating layer, each based on a total of 100wt% of the anode active material, and the remainder may be carbon particles.
- the elements of the anode active material may exhibit the above-described effect.
- a particles diameter of the carbon particles, a thickness of the first carbon coating layer, a thickness of the silicon coating layer, and a thickness of the second carbon coating layer may satisfy the following ranges.
- the carbon particles may have a particle diameter of 5 ⁇ m to 20 ⁇ m.
- the first carbon coating layer may have a thickness of 5 nm to 200 nm.
- the silicon coating layer may have a thickness of 20 nm to 60 nm.
- the second carbon coating layer may have a thickness of 5 nm to 200 nm.
- volume expansion and side reactions of the silicon coating layer may be controlled by varying the amounts and thicknesses of the first carbon coating layer within the above limited ranges.
- capacity of the anode active material exhibited by the silicon coating layer may be controlled.
- the anode active material may have improved capacity.
- the first carbon coating layer may provide an increased specific surface area to carbon particles when coated thereon, compared to the other spherical carbon particles not coated by the first carbon coating layer.
- This increased specific surface area may provide sites for deposition and/or coating of a larger amount of silicon, and may also serve as a support (i.e., implant) stably fixing the deposited and/or coated silicon. This is due to, as described above, that silicon may be deposited/or coated inside or over pores in the first carbon coating layer.
- the carbon particles after the formation of the first coating layer were found to have a considerably increased BET specific surface area, compared to graphite particles without any coatings thereon (i.e., before formation of the first coating layer).
- This increase in BET specific surface area may mean increased porosity
- the BET specific surface area may be decreased after the formation of the first carbon coating layer.
- using the chemical vapor deposition method may exhibit improved battery characteristics. This is attributed to unnecessary micropores of spherical graphite being clogged in advance, which leads to silicon using sufficiently large pores as void spaces and coating only the large pores and a surface of the graphite.
- the first carbon coating layer may reduce the BET specific surface area of graphite by blocking unnecessary pores in the graphite, and may serve as a conduction path and buffer of silicon by being coated on the surface of the graphite.
- the first carbon coating layer may be uniformly coated on the surfaces of the carbon particles.
- the second carbon coating layer may also be uniformly coated on a surface of the silicon coating layer.
- the expression "uniformly coated” used herein may refer to the surfaces of the carbon particles and the silicon coating layer being densely coated so as not to be exposed.
- the carbon particles may include graphite, amorphous carbon, or a combination thereof.
- the carbon particles may be graphite.
- the first carbon coating layer and the outermost second carbon coating layer may include amorphous carbon.
- a method of preparing an anode active material for a lithium secondary battery including: preparing carbon particles having a spherical shape; forming a first carbon coating layer on surfaces of the carbon particles; forming, on the first carbon coating layer, a silicon coating layer including silicon nanoparticles; and forming a second carbon coating layer on the silicon coating layer.
- a carbon/silicon composite having a capacity of 400 mAh/g to 800 mAh/g may be synthesized.
- This carbon/silicon composite may have the same characteristics (for example, composition, thickness, etc.) as that described above in connection with the embodiments of the anode active material.
- FIG. 1 is a flow diagram of a method of preparing an anode active material, according to an embodiment.
- the carbon particles coated by the first coating layer may be provided with an increased or decreased BET specific surface area, compared to the other spherical carbon particles not coated by the first coating layer.
- Required battery characteristics may be controlled according to such an increased or reduced specific surface area of the carbon particles. This has been sufficiently described above, and thus a detailed description thereof will be omitted.
- the forming of the first coating layer on the surfaces of the carbon particles may be performed using a sol-gel method or a chemical vapor deposition method.
- the forming of the silicon coating layer including silicon nanoparticles on the first carbon coating layer may be performed using a chemical vapor deposition method.
- a silicon-based precursor for example, silane (SiH 4 ), dichlorosilane (SiH 2 Cl 2 ), silicon tetrafluoride (SiF 4 ), silicon tetrachloride (SiCl 4 ), methylsilane (CH 3 SiH 3 ), disilane (Si 2 H 6 ), or a combination thereof may be used.
- silicon-based precursors may be in a liquid or vapor state.
- the silicon-based precursor in a liquid or vapor state may be mixed with a gas such as hydrogen (H 2 ), argon (Ar), or nitrogen (N 2 ), and then used in chemical vapor deposition.
- a gas such as hydrogen (H 2 ), argon (Ar), or nitrogen (N 2 ), and then used in chemical vapor deposition.
- the silicon nanoparticles in the silicon coating layer may be amorphous, and the silicon coating layer may be deposited in a mixed form of a film and an island. Accordingly, capacity per unit weight of silicon and coulombic efficiency may be improved.
- the forming of the second carbon coating layer on the silicon coating layer may be performed using a sol-gel method or a chemical vapor deposition method.
- a carbon precursor selected from the group consisting of a rayon-based carbon precursor, a PAN-based carbon precursor, a pitch-based carbon precursor, and a combination thereof and a carbon vapor deposition method are used, the second carbon coating layer may be uniformly coated on a surface of the silicon coating layer as described above.
- Uncoated graphite (bare graphite) was used as an anode active material.
- An anode active material including a silicon coating layer on graphite was prepared by chemical vapor deposition at a temperature of 550°C from 50 g of the graphite of Comparative Example 1 and SiH 4 (gas) at a rate of 50 sccm for 60 minutes. Then, through pyrolysis of C 2 H 2 (gas) at a rate of about 1.5 L/min at a temperature of 900°C, a carbon layer was coated on the silicon coating layer of the anode active material.
- the obtained anode active material included 95wt% of graphite, 4wt% of silicon, and 1wt% of carbon contained in the outermost carbon layer, based on a total weight of the anode active material.
- Carbon coating was performed on the anode active material of Comparative Example 1 by using a chemical vapor deposition method or a sol-gel method.
- the chemical vapor deposition method 50 g of the spherical graphite was heated under an inter gas atmosphere (N 2 ) from room temperature to 900°C at a rate of 5°C/min. When the temperature reached 900°C, then ethylene gas was flowed at 1.5L/min for 30 minutes, thereby forming a first carbon coating layer on the spherical graphite.
- the spherical graphite including the first carbon coating layer had a decreased BET specific surface area of 3.3 m 2 /g.
- sucrose was used as a carbon precursor. 5 g of sucrose was dissolved in a 9:1 mixed solvent of water and ethanol. When sucrose is subjected to carbonization under a high-temperature inert atmosphere, only 30% of a total added amount of sucrose remains as carbon. Accordingly, to obtain only 3wt% of carbon based on a total weight of graphite and carbon, 5 g of sucrose with respect to 50 g of graphite was sufficient. In this experiment, after sucrose was sufficiently dissolved in the mixed solvent of water and ethanol, 50 g of graphite was added while continuously string to evaporate only the solution at nearly 100°C.
- the thus-obtained solid was loaded into a furnace under an inert atmosphere, and then subjected to carbonization at 900°C for 10 minutes. 99% or greater of the obtained powder was filtered through a micro sieve.
- SEM scanning electron microscopy
- TEM transmission electron microscopy
- the obtained anode active material was found to include 86.5 wt% of graphite, 2wt% to 3wt% of the first carbon coating layer, 8.5wt% of silicon, and 2wt% to 3wt% of the outermost carbon coating layer, based on a total weight of the anode active material.
- the prepared anode active material, a conducting agent, and a binder were used in a ratio of 95.8: 1: 3.2 to prepare a slurry.
- the conducting agent used was Super-P.
- As the binder a mixture of styrene butadiene rubber (SBR) and sodium carboxymethyl cellulose (CMC) in a weight ratio of 1.5: 1.7 was used.
- the slurry was uniformly coated on a copper foil, dried in a 80°C oven for 2 hours, roll-pressed, and then further dried in a 110°C vacuum oven for 12 hours to manufacture an anode plate.
- a CR2016 coin-type half cell was manufactured using the above-manufactured anode plate, a lithium coil as a counter electrode, a porous polyethylene membrane as a separator, and a liquid electrolyte containing 1.0M LiPF 6 dissolved in a 7:3 (by volume) mixed solvent of diethyl carbonate (DEC) and fluoroethylene carbonate (FEC) according to a commonly known manufacturing process.
- DEC diethyl carbonate
- FEC fluoroethylene carbonate
- Table 1 shows data of the particles according to the above-described Example when the chemical vapor deposition method was used.
- Table 2 Data of Example 0 min 30 min 1 hr 2 hr BET (m 2 /g) 5.28 3.2298 3.0182 2.3395 Pore volume (cm 3 /g) 0.022 0.014338 0.012451 0.008448
- Table 2 shows changes in BET when the first carbon coating layer was formed on the graphite by using chemical vapor deposition, not the sol-gel method.
- the bare graphite had a BET specific surface area of 5.28 m 2 /g, while the particles had increased BET specific surface areas merely after the coating of the first carbon coating layers. It was also found that when the chemical vapor deposition method was used, the BET specific surface areas of the particles were decreased to the specific surface area of the graphite, as shown in Table 2.
- FIG. 2 shows analysis data of the anode active materials of Example.
- the upper left image is a scanning electron microscope (SEM) image at a low magnification of spherical graphite as mother material
- the upper middle image is a SEM image at a high magnification of a particle after all the treatments (G+C+Si+C) according to Example
- the upper right image is an EDS mapping image of the upper middle image.
- quadrant 1 (upper right) is an image showing the presence of oxygen
- quadrant 2 (upper left) is an image showing the presence of carbon
- quadrant 3 (lower left) is an image showing the presence of Si
- quadrant 4 (lower right) is an image showing all the three elements. From these images, it was found that Si was under the second carbon coating.
- a graph in the lower middle of FIG. 2 shows the intensities of the elements obtained from the EDS mapping.
- FIG. 3 shows transmission electron microscope (TEM) images of the particles obtained according to Example.
- TEM transmission electron microscope
- FIG. 3 shows high-magnification TEM images of cross-section samples of the final spherical particles prepared by cutting using focused ion beams (FIBs).
- FIBs focused ion beams
- the left image is a SEM image showing sampling for TEM from the final spherical graphite (G+C+Si+C) by using FIBs.
- the final spherical graphite included the graphite layer, the first carbon coating layer on the graphite layer, the Si coating layer on the first carbon coating layer (a mixed structure of crystalline and amorphous forms), and the second carbon coating layer as the outermost layer, as shown in the upper right images.
- a titanium (Ti) coating layer on the second carbon coating layer as a protection layer which is usually formed to protect the surface of a sample from strong FIBs used to cut the sample, is irrelevant to the examples of the present disclosure.
- the first carbon coating layer was coated on the spherical graphite surface and at the same time partially inside the spherical graphite, and silicon was deposited thereon. As shown in the lower right image of FIG. 3 , small pores in the graphite were also filled by the first carbon coating layer. In this case, silicon was deposited on the surface and inside of the graphite, except for the pore region, indicating that a partial presence of a concentration gradient layer of silicon and carbon.
- FIG. 4 shows high-magnification TEM images and EDS results.
- the upper right, high-magnification TEM image shows that silicon was coated on both the surface and inside of the graphite, but not in the inner pores of the graphite (regions with slash lines in the TEM image), as being filled with the first carbon coating layer.
- the second carbon coating layer (green) appears under the Ti protection layer (pink).
- the Si layer under the second carbon coating layer, and the mixed layer of Si and C also appear.
- the mixed layer of Si and C is due to the first carbon coating layer serving as a support layer of silicon deposited thereon.
- the presence of carbon (C) from graphite appears under the mixed layer of SI and C.
- FIG. 5 shows the results of energy dispersive X-ray (EDX) line mapping.
- FIG. 6 shows the results of X-ray diffraction (XRD) analysis.
- GCS graphite
- C first carbon coating layer
- S silicon
- FIG. 7 is a graph showing lifetime characteristics and coulombic efficiency with respect to the number of cycles in a cell according to Example.
- the X-axis denotes the number of cycles
- the Y-axis on the left denotes charge capacity
- the Y-axis on the right denotes coulombic efficiency. Referring to FIG. 7 , the cell according to Example was found to have desired cell characteristics.
- FIG. 8 shows evaluation data of capacity retention rate with respect to the number of cycles.
- the table in FIG. 8 shows the levels of volume expansion (%) after 50 cycles relative to before the cycles, when the first carbon coating layer was or was not formed, wherein the levels of volume expansion were evaluated by measuring the thicknesses of an electrode plate taken from the cell before and after 50 cycles.
- a graph in red denotes when the first carbon coating layer was not formed (Graphite+Si+Carbon, Comparative Example 2), and a graph in orange denotes when the first carbon coating layer was formed (Example).
- the final material including the first carbon coating layer (Graphite +Carbon +Si +Carbon, Example) were found to have improved volume expansions characteristics by about 20%, compared to that of Comparative Example 2.
- FIG. 9 shows evaluation data of rate characteristics.
- Graphite denotes a sample of Comparative Example 1
- UNIST 600 class denotes a sample of Example
- Lithiation denotes high-rate charge characteristics at 0.5C, 1C. 2C, 3C, and 5C
- De-lithiation denotes high-rate discharge characteristics at 0.5C, 1C, 2C, 3C, and 5C.
- the X-axis denotes the number of cycles
- the Y-axis denotes normalized capacity retention.
- Graphite has a reversible capacity (i.e., non-theoretical actual capacity) of about 357mAh/g as a result of normalization.
- the material of Example was found to have a reversible capacity of about 600mAh/g. Based on these two initial reversible capacities (100%), a degree of capacity drop (%) with respect to the initial reversible capacity with increasing C-rates was evaluated. As a result, the cell of Example was found to have considerably improved battery characteristics.
Abstract
Description
- The present disclosure relates to an anode active material for a lithium secondary battery, a preparation method thereof, and a lithium secondary battery including the anode active material.
- A lithium secondary battery, which is charged and discharged through oxidation/reduction of lithium ions, includes a cathode, an anode, an ion exchange membrane between the cathode and the anode, and an electrolyte.
- For systems that require large-capacity batteries, such as electric vehicles, there is a need to increase capacity of an anode active material used in such a lithium secondary battery and increase output characteristics and lifetime characteristics of the lithium secondary battery. To this end, there is a need for development of a stable alloy-based anode material having a high capacity, instead of conventional carbonaceous anode materials.
- A conventional carbonaceous anode active material has merely a theoretical capacity of about 372 mAh/g, and significantly reduced output characteristics, particularly in a high-rate charging condition, due to a mechanism of intercalation and deintercalation of lithium ions in a carbon interlayer during charging and discharging.
- An alloy-based material that is currently under research also has fairly low electrical conductivity and may undergo considerable volume expansions during charging and discharging, leading to severe damage of electrode plates and a sharp reduction in capacity. Therefore, there are difficulties in commercializing the alloy-based material.
- The present invention provides an anode active material for a lithium secondary battery, having greater capacity than conventional commercialized carbonaceous anode active materials and improved lifetime and output characteristics, and a method of preparing the anode active material.
- According to an aspect of the present invention, an anode active material for a lithium secondary battery includes: carbon particles having a spherical shape; a first carbon coating layer present on surfaces of the carbon particles; a silicon coating layer present on the first carbon coating layer and including silicon nanoparticles; and a second carbon coating layer present on the silicon coating layer.
- The carbon particles having the first carbon coating layer thereon may have an 10% or greater increased Brunauer-Emmett-Teller (BET) specific surface area with respect to a BET specific surface area of the carbon particles having the spherical shape.
- The carbon particles having the first carbon coating layer thereon may have an 10% or greater reduced Brunauer-Emmett-Teller (BET) specific surface area with respect to a BET specific surface area of the carbon particles having the spherical shape.
- The silicon nanoparticles may be semicrystalline.
- The first carbon coating layer may partially include a mixed layer of silicon and carbon.
- The mixed layer of silicon and carbon may have a concentration gradient in which an amount of silicon decreases in the direction of a core.
- The silicon coating layer present on the first carbon coating layer may be in a mixed form of a film and an island.
- A content ratio of silicon to carbon may be about 3:97 to about 20:80, with respect to a total weight of the anode active material.
- The anode active material may include 2wt% to 6wt% of the first carbon coating layer, 4wt% to 20wt% of the silicon coating layer, and 1.5wt% to 10wt% of the second carbon coating layer, each based on a total of 100wt% of the anode active material, and the remainder may be the carbon particles.
- The carbon particles may include graphite, amorphous carbon, or a combination thereof.
- The carbon particles may have a particle diameter of 5 µm to 20 µm.
- The first carbon coating layer may have a thickness of 5 nm to 200 nm.
- The silicon coating layer may have a thickness of 20 nm to 60 nm.
- The second carbon coating layer may have a thickness of 5 nm to 200 nm.
- According to an aspect of the present invention, a method of preparing an anode active material for a lithium secondary battery includes: preparing carbon particles having a spherical shape; forming a first carbon coating layer on surfaces of the carbon particles; forming, on the first carbon coating layer, a silicon coating layer including silicon nanoparticles; and forming a second carbon coating layer on the silicon coating layer.
- The forming of the first carbon coating layer on the surfaces of the carbon particles may be performed using a sol-gel method.
- The forming of the first carbon coating layer on the surfaces of the carbon particles may be performed using a chemical vapor deposition method.
- In the forming of the silicon coating layer including silicon nanoparticles on the first carbon coating layer, the silicon nanoparticles may be amorphous. In the forming of the silicon coating layer including silicon nanoparticles on the first carbon coating layer, the silicon coating layer may be deposited in a mixed form of a film and an island.
- In the forming of the silicon coating layer including silicon nanoparticles on the first carbon coating layer, a silicon-based precursor, for example, silane (SiH4), dichlorosilane (SiH2Cl2), silicon tetrafluoride (SiF4), silicon tetrachloride (SiCl4), methylsilane (CH3SiH3), disilane (Si2H6), or a combination thereof may be used.
- The forming of the second carbon coating layer on the silicon coating layer may be performed using a physical milling method, a sol-gel method, or a chemical vapor deposition method.
- When the forming of the second carbon coating layer on the silicon coating layer is performed using a chemical vapor deposition method, a carbon precursor selected from the group consisting of a rayon-based carbon precursor, a PAN-based carbon precursor, a pitch-based carbon precursor, and a combination thereof may be used.
- According to an aspect of the present invention, a lithium secondary battery includes: a cathode; an anode; and an electrolyte, wherein the anode include the anode active material according to any of the embodiments.
- As described above, according to the one or more embodiments, an anode active material for a lithium secondary battery, having improved lifetime characteristics and output characteristics, and a method of preparing the anode active material may be obtained.
-
-
FIG. 1 is a flow diagram of a method of preparing an anode active material according to an embodiment. -
FIG. 2 shows evaluation data of anode active materials according to Example. -
FIG. 3 shows transmission electron microscope (TEM) images of a particle according to Example. -
FIG. 4 shows high-magnification TEM images and energy dispersive spectroscopy (EDS) results. -
FIG. 5 shows the results of energy dispersive X-ray (EDX) line mapping. -
FIG. 6 shows the results of X-ray diffraction (XRD) analysis. -
FIG. 7 is a graph showing lifetime characteristics and coulombic efficiency with respect to the number of cycles in a cell according to Example. -
FIG. 8 shows evaluation data of capacity retention rate with respect to the number of cycles. -
FIG. 9 shows evaluation data of rate characteristics. - Hereinafter, embodiments of the present disclose will be described in greater detail. In this regard, embodiments described herein should be considered in a descriptive sense only and not for purposes of limitation. The present embodiments may have different forms and should not be construed as being limited to the descriptions set forth herein.
- According to an aspect of the present disclosure, there is provided an anode active material for a lithium secondary battery, including: carbon particles having a spherical shape; a first carbon coating layer present on surfaces of the carbon particles; a silicon coating layer present on the first carbon coating layer and including silicon nanoparticles; and a second carbon coating layer present on the silicon coating layer.
- In some embodiments, the carbon particles having the first carbon coating layer thereon have an about 10% or greater increased or reduced Brunauer-Emmett-Teller (BET) specific surface area with respect to a BET specific surface area of the carbon particles not having the first carbon coating layer thereon.
- The anode active material according to one or more embodiments may have a carbon/silicon composite structure. When this carbon/silicon composite is formed from a blended slurry prepared using heterogeneous materials including a carbonaceous anode material and amorphous silicon powder, problems such as phase separation and dispersion may be resolved.
- A considerably increased specific surface area of the spherical carbon particles (for example, graphite), due to the first carbon coating layer, may be made the best use of. The carbon/silicon composite may be implemented by depositing and/or coating silicon inside or over pores in the first carbon coating layer through chemical vapor deposition and then forming the second carbon coating layer thereon.
- In some embodiments, in forming the first carbon coating layer on the spherical carbon particles, a sol-gel method may be used to obtain a structure having further increased Brunauer-Emmett-Teller (BET) specific surface area and porosity.
- In some other embodiments, in forming the first carbon coating layer on the carbon particles having the spherical shape, a chemical vapor deposition method may be used to obtain a structure having further decreased BET specific surface area and porosity.
- The method of forming the first carbon coating layer may be appropriately selected according to desired characteristics of the anode active material.
- By previously being coated inside and on surfaces of the spherical carbon particles, carbon particles may serve as a support layer for silicon particles that are to be deposited thereon, improving electrical conductivity and preventing inner sites of the spherical carbon particles from unnecessarily being coated with silicon, so as to mitigate volume expansion of a battery during charging and discharging.
- The carbon particles having the first carbon coating layer thereon may have, for example, a BET surface area of 2 m2/g to 50 m2/g, and in some embodiments, 2 m2/g to 7 m2/g, and in some other embodiments, 8 m2/g to 50 m2/g. However, embodiments are not limited thereto, and the BET surface area of the carbon particles may be varied within these ranges.
- Accordingly, the carbon/silicon composite may be implemented to have a structure facilitating diffusion of lithium ions into the anode active material and at the same time providing high capacity.
- The second carbon coating layer as an outermost layer may provide electron transfer paths between or inside particles in manufacturing an electrode plate and thus to improve conductivity, and may control volume change of silicon during charging and discharging, thus improving stability of the electrode plate.
- The carbon/silicon composite as described above may have higher capacity, relative to a conventionally commercialized carbonaceous anode material, and improved lifetime and output characteristics.
- Hereinafter, an anode active material for a lithium secondary battery, having the carbon/silicon composite structure as described above, will be described in greater detail.
- First, the silicon nanoparticles may be amorphous. The amorphous silicon nanoparticles may have a large capacity per weight of the particles, significantly reduced stress from volume expansion during charging (i.e., alloying with lithium), compared to crystalline silicon nanoparticles, and fast speeds of alloying and dealloying with lithium, which is advantageous in terms of charging and discharging rates.
- The silicon coating layer on the first carbon coating layer may be in a form of a film, an island, or a mixed form thereof. As will be described later, the silicon coating layer may be formed, by a chemical vapor deposition method, on the first carbon coating layer in a form of a film, an island, or a combination thereof, using an appropriate silicon-based precursor.
- For example, when using the chemical vapor deposition method, the silicon coating layer may be formed in the form of an island at the beginning. The island form is an appropriate form to cope with volume expansion of the silicon nanoparticles included in the silicon coating layer.
- As the deposition amount is increased, the silicon coating layer may be formed as a film and then finally as a mixed form of an island and a film at the end of the deposition. This may lead to an improved capacity per weight of the silicon particles and improved coulombic efficiency.
- Unlike this, when a physical deposition method such as ball milling is used, the silicon nanoparticles may be simply adhered onto the first carbon coating layer by a strong physical force while source materials are mixed. In this case, it is nearly impossible to make the silicon nanoparticles adhere while uniformly controlling a degree of distribution. Furthermore, since the source materials are mixed and ground at the same time, the carbon material may be damaged, causing performance degradation when used in a battery.
- A content ratio of silicon to carbon may be 3:97 to 20:80, with respect to a total weight of the anode active material. When the content ratio of silicon to carbon satisfies this range, the anode active material may exhibit a high capacity of 400 mAh/g to 800 mAh/g.
- In some embodiments, the anode active material may include 2wt% to 6wt% of the first carbon coating layer, 4wt% to 20wt% of the silicon coating layer, 1.5wt% to 10wt% of the second carbon coating layer, each based on a total of 100wt% of the anode active material, and the remainder may be carbon particles. When each element of the anode active material satisfies these ranges, the elements of the anode active material may exhibit the above-described effect.
- When each of the elements satisfies the above ranges, a particles diameter of the carbon particles, a thickness of the first carbon coating layer, a thickness of the silicon coating layer, and a thickness of the second carbon coating layer may satisfy the following ranges.
- The carbon particles may have a particle diameter of 5 µm to 20 µm.
- The first carbon coating layer may have a thickness of 5 nm to 200 nm.
- The silicon coating layer may have a thickness of 20 nm to 60 nm.
- The second carbon coating layer may have a thickness of 5 nm to 200 nm.
- Since the silicon coating layer is located between the first carbon coating layer and the second carbon coating layer, volume expansion and side reactions of the silicon coating layer may be controlled by varying the amounts and thicknesses of the first carbon coating layer within the above limited ranges.
- Furthermore, by varying the amount and thickness of the silicon coating layer within the above limited ranges, capacity of the anode active material exhibited by the silicon coating layer may be controlled. In particular, as the amount and thickness of the silicon coating layer are increased, the anode active material may have improved capacity.
- In some embodiments, the first carbon coating layer may provide an increased specific surface area to carbon particles when coated thereon, compared to the other spherical carbon particles not coated by the first carbon coating layer. This increased specific surface area may provide sites for deposition and/or coating of a larger amount of silicon, and may also serve as a support (i.e., implant) stably fixing the deposited and/or coated silicon. This is due to, as described above, that silicon may be deposited/or coated inside or over pores in the first carbon coating layer.
- In some embodiments, when a sol-gel method is used, as a result of measuring BET specific surface areas before and after the formation of the first coating layer, the carbon particles after the formation of the first coating layer were found to have a considerably increased BET specific surface area, compared to graphite particles without any coatings thereon (i.e., before formation of the first coating layer). This increase in BET specific surface area may mean increased porosity
In some other embodiments, when a chemical vapor deposition method is used, the BET specific surface area may be decreased after the formation of the first carbon coating layer. In a certain case, using the chemical vapor deposition method may exhibit improved battery characteristics. This is attributed to unnecessary micropores of spherical graphite being clogged in advance, which leads to silicon using sufficiently large pores as void spaces and coating only the large pores and a surface of the graphite. - That is, the first carbon coating layer may reduce the BET specific surface area of graphite by blocking unnecessary pores in the graphite, and may serve as a conduction path and buffer of silicon by being coated on the surface of the graphite.
- The first carbon coating layer may be uniformly coated on the surfaces of the carbon particles. The second carbon coating layer may also be uniformly coated on a surface of the silicon coating layer. The expression "uniformly coated" used herein may refer to the surfaces of the carbon particles and the silicon coating layer being densely coated so as not to be exposed.
- The carbon particles may include graphite, amorphous carbon, or a combination thereof. For example, the carbon particles may be graphite. Independent of this, the first carbon coating layer and the outermost second carbon coating layer may include amorphous carbon.
- According to another aspect of the present disclosure, there is provided a method of preparing an anode active material for a lithium secondary battery, the method including: preparing carbon particles having a spherical shape; forming a first carbon coating layer on surfaces of the carbon particles; forming, on the first carbon coating layer, a silicon coating layer including silicon nanoparticles; and forming a second carbon coating layer on the silicon coating layer.
- Through this method, a carbon/silicon composite having a capacity of 400 mAh/g to 800 mAh/g may be synthesized. This carbon/silicon composite may have the same characteristics (for example, composition, thickness, etc.) as that described above in connection with the embodiments of the anode active material.
- Hereinafter, each step of the method will be described in greater detail, and the overlapping description of the carbon/silicon composite will be omitted.
-
FIG. 1 is a flow diagram of a method of preparing an anode active material, according to an embodiment. - Through the forming of the first coating layer on the surfaces of the carbon particles, the carbon particles coated by the first coating layer may be provided with an increased or decreased BET specific surface area, compared to the other spherical carbon particles not coated by the first coating layer. Required battery characteristics may be controlled according to such an increased or reduced specific surface area of the carbon particles. This has been sufficiently described above, and thus a detailed description thereof will be omitted.
- In some embodiments, the forming of the first coating layer on the surfaces of the carbon particles may be performed using a sol-gel method or a chemical vapor deposition method.
- The forming of the silicon coating layer including silicon nanoparticles on the first carbon coating layer may be performed using a chemical vapor deposition method.
- In this case, in a deposition step of the silicon coating layer, a silicon-based precursor, for example, silane (SiH4), dichlorosilane (SiH2Cl2), silicon tetrafluoride (SiF4), silicon tetrachloride (SiCl4), methylsilane (CH3SiH3), disilane (Si2H6), or a combination thereof may be used. These silicon-based precursors may be in a liquid or vapor state.
- For example, after being vaporized, the silicon-based precursor in a liquid or vapor state may be mixed with a gas such as hydrogen (H2), argon (Ar), or nitrogen (N2), and then used in chemical vapor deposition.
- When such a chemical vapor deposition method is used, the silicon nanoparticles in the silicon coating layer may be amorphous, and the silicon coating layer may be deposited in a mixed form of a film and an island. Accordingly, capacity per unit weight of silicon and coulombic efficiency may be improved.
- The forming of the second carbon coating layer on the silicon coating layer may be performed using a sol-gel method or a chemical vapor deposition method. For example, when a carbon precursor selected from the group consisting of a rayon-based carbon precursor, a PAN-based carbon precursor, a pitch-based carbon precursor, and a combination thereof and a carbon vapor deposition method are used, the second carbon coating layer may be uniformly coated on a surface of the silicon coating layer as described above.
- One or more embodiments of the present disclosure will now be described in detail with reference to the following examples. However, these examples are only for illustrative purposes and are not intended to limit the scope of the one or more embodiments of the present disclosure.
- Uncoated graphite (bare graphite) was used as an anode active material.
- An anode active material including a silicon coating layer on graphite was prepared by chemical vapor deposition at a temperature of 550°C from 50 g of the graphite of Comparative Example 1 and SiH4 (gas) at a rate of 50 sccm for 60 minutes. Then, through pyrolysis of C2H2 (gas) at a rate of about 1.5 L/min at a temperature of 900°C, a carbon layer was coated on the silicon coating layer of the anode active material. The obtained anode active material included 95wt% of graphite, 4wt% of silicon, and 1wt% of carbon contained in the outermost carbon layer, based on a total weight of the anode active material.
- Carbon coating was performed on the anode active material of Comparative Example 1 by using a chemical vapor deposition method or a sol-gel method. In the chemical vapor deposition method, 50 g of the spherical graphite was heated under an inter gas atmosphere (N2) from room temperature to 900°C at a rate of 5°C/min. When the temperature reached 900°C, then ethylene gas was flowed at 1.5L/min for 30 minutes, thereby forming a first carbon coating layer on the spherical graphite. The spherical graphite including the first carbon coating layer had a decreased BET specific surface area of 3.3 m2/g.
- In the sol-gel method, sucrose was used as a carbon precursor. 5 g of sucrose was dissolved in a 9:1 mixed solvent of water and ethanol. When sucrose is subjected to carbonization under a high-temperature inert atmosphere, only 30% of a total added amount of sucrose remains as carbon. Accordingly, to obtain only 3wt% of carbon based on a total weight of graphite and carbon, 5 g of sucrose with respect to 50 g of graphite was sufficient. In this experiment, after sucrose was sufficiently dissolved in the mixed solvent of water and ethanol, 50 g of graphite was added while continuously string to evaporate only the solution at nearly 100°C. The thus-obtained solid was loaded into a furnace under an inert atmosphere, and then subjected to carbonization at 900°C for 10 minutes. 99% or greater of the obtained powder was filtered through a micro sieve. As a result of scanning electron microscopy (SEM) or transmission electron microscopy (TEM) on cross-sections of the powder, the surface and inside of the graphite was found as being coated with carbon.
- Experiments were carried out using a range of amounts of carbon as follows.
- Next, chemical vapor deposition from SiH4 (gas) at a rate of about at 50sccm for 60 min was performed to form a silicon coating layer on the graphite.
- Through pyrolysis of C2H2 (gas) at a rate of 1.5L/min at a temperature of 900°C, an anode active material having a carbon layer coated on the silicon coating layer was prepared.
- The obtained anode active material was found to include 86.5 wt% of graphite, 2wt% to 3wt% of the first carbon coating layer, 8.5wt% of silicon, and 2wt% to 3wt% of the outermost carbon coating layer, based on a total weight of the anode active material.
- The prepared anode active material, a conducting agent, and a binder were used in a ratio of 95.8: 1: 3.2 to prepare a slurry. The conducting agent used was Super-P. As the binder, a mixture of styrene butadiene rubber (SBR) and sodium carboxymethyl cellulose (CMC) in a weight ratio of 1.5: 1.7 was used.
- The slurry was uniformly coated on a copper foil, dried in a 80°C oven for 2 hours, roll-pressed, and then further dried in a 110°C vacuum oven for 12 hours to manufacture an anode plate.
- A CR2016 coin-type half cell was manufactured using the above-manufactured anode plate, a lithium coil as a counter electrode, a porous polyethylene membrane as a separator, and a liquid electrolyte containing 1.0M LiPF6 dissolved in a 7:3 (by volume) mixed solvent of diethyl carbonate (DEC) and fluoroethylene carbonate (FEC) according to a commonly known manufacturing process.
- Specific surface areas and porosities of the bare graphite of Comparative Example 1 and particles having first carbon coating layers (prepared in the above-described Example) before the silicon deposition were measured. The results are shown in Table 1.
[Table 1] Graphite coated Carbon by citric acid Data Specific Capa. (mAh/g) ICE (%) BET (m2/g) Graphite 365 91.4 5.28 Carbon coating 0.75wt% (vs Graphite) 373 90.4 8.99 Carbon coating 1.5wt% (vs Graphite) 375 89.7 12.93 Carbon coating 3wt% (vs Graphite) 372 87.7 16.85 Carbon coating 4.5wt% (vs Graphite) 370 83.8 34.61 Carbon coating 6wt% (vs Graphite) 370 82.2 42.36 - Referring to Table 1, it was found that when carbon coating was performed using the sol-gel method, the specific surface areas of the particles were increased. Table 2 shows data of the particles according to the above-described Example when the chemical vapor deposition method was used.
[Table 2] Data of Example 0 min 30 min 1 hr 2 hr BET (m2/g) 5.28 3.2298 3.0182 2.3395 Pore volume (cm3/g) 0.022 0.014338 0.012451 0.008448 - That is, Table 2 shows changes in BET when the first carbon coating layer was formed on the graphite by using chemical vapor deposition, not the sol-gel method.
- Referring to Tables 1 and 2, the bare graphite had a BET specific surface area of 5.28 m2/g, while the particles had increased BET specific surface areas merely after the coating of the first carbon coating layers. It was also found that when the chemical vapor deposition method was used, the BET specific surface areas of the particles were decreased to the specific surface area of the graphite, as shown in Table 2.
-
FIG. 2 shows analysis data of the anode active materials of Example. - In
FIG. 2 , the upper left image is a scanning electron microscope (SEM) image at a low magnification of spherical graphite as mother material, the upper middle image is a SEM image at a high magnification of a particle after all the treatments (G+C+Si+C) according to Example, and the upper right image is an EDS mapping image of the upper middle image. - In the EDS mapping image, quadrant 1 (upper right) is an image showing the presence of oxygen, quadrant 2 (upper left) is an image showing the presence of carbon, quadrant 3 (lower left) is an image showing the presence of Si, and quadrant 4 (lower right) is an image showing all the three elements. From these images, it was found that Si was under the second carbon coating.
- A graph in the lower middle of
FIG. 2 shows the intensities of the elements obtained from the EDS mapping. -
FIG. 3 shows transmission electron microscope (TEM) images of the particles obtained according to Example. In particular,FIG. 3 shows high-magnification TEM images of cross-section samples of the final spherical particles prepared by cutting using focused ion beams (FIBs). - In
FIG. 3 , the left image is a SEM image showing sampling for TEM from the final spherical graphite (G+C+Si+C) by using FIBs. When the surface and inside of the final spherical graphite were observed using TEM, it was found that the final spherical graphite included the graphite layer, the first carbon coating layer on the graphite layer, the Si coating layer on the first carbon coating layer (a mixed structure of crystalline and amorphous forms), and the second carbon coating layer as the outermost layer, as shown in the upper right images. - A titanium (Ti) coating layer on the second carbon coating layer, as a protection layer which is usually formed to protect the surface of a sample from strong FIBs used to cut the sample, is irrelevant to the examples of the present disclosure.
- As shown in
FIG. 3 , it was found that the first carbon coating layer was coated on the spherical graphite surface and at the same time partially inside the spherical graphite, and silicon was deposited thereon. As shown in the lower right image ofFIG. 3 , small pores in the graphite were also filled by the first carbon coating layer. In this case, silicon was deposited on the surface and inside of the graphite, except for the pore region, indicating that a partial presence of a concentration gradient layer of silicon and carbon. -
FIG. 4 shows high-magnification TEM images and EDS results. - As shown in the upper left image, it is clear that there was a high contrast (light and shade difference) between carbon and silicon. The dark color (dark gray or gray) indicates carbon, and the light color (near white) indicates silicon.
- In summary, the upper right, high-magnification TEM image shows that silicon was coated on both the surface and inside of the graphite, but not in the inner pores of the graphite (regions with slash lines in the TEM image), as being filled with the first carbon coating layer.
- Referring to the upper right image as results of the EDS Mapping, the second carbon coating layer (green) appears under the Ti protection layer (pink). The Si layer under the second carbon coating layer, and the mixed layer of Si and C (yellow fluorescent regions) also appear.
- The mixed layer of Si and C is due to the first carbon coating layer serving as a support layer of silicon deposited thereon. The presence of carbon (C) from graphite appears under the mixed layer of SI and C.
-
FIG. 5 shows the results of energy dispersive X-ray (EDX) line mapping. - Referring to an element analysis graph of
FIG. 5 (lower part), the presence of Ti, C, Si, and C was identified in the stated order from left to right, and there are C-Si mixed regions (two regions denoted by circles) at both edges of the Si region, the left one corresponding to the second carbon coating layer, the right one corresponding to the first carbon coating layer. It is assumed that the presence of the C-Si mixed regions is due to the increase specific surface area of the carbon (C) layer. -
FIG. 6 shows the results of X-ray diffraction (XRD) analysis. - In
FIG. 6 , "GCS" denotes a sample having a structure of graphite (G) + first carbon coating layer (C) + silicon (S) having a capacity of about 600mAh/g. Referring toFIG. 6 , in the GCS sample, the intensities of only graphite peaks were detected, but not any peak of amorphous silicon (Si). - However, in a GCSC sample including the second carbon coating layer, silicon peaks were detected. This is attributed to that the amorphous silicon was partially changed into crystalline form during deposition of the second carbon coating layer at about 900°C.
- That is, it was found that according to Example, silicon as deposited on first carbon coating layer was amorphous but changed into semicrystalline form during the formation of the second carbon coating layer.
-
FIG. 7 is a graph showing lifetime characteristics and coulombic efficiency with respect to the number of cycles in a cell according to Example. The X-axis denotes the number of cycles, the Y-axis on the left denotes charge capacity, and the Y-axis on the right denotes coulombic efficiency. Referring toFIG. 7 , the cell according to Example was found to have desired cell characteristics. -
FIG. 8 shows evaluation data of capacity retention rate with respect to the number of cycles. - The table in
FIG. 8 shows the levels of volume expansion (%) after 50 cycles relative to before the cycles, when the first carbon coating layer was or was not formed, wherein the levels of volume expansion were evaluated by measuring the thicknesses of an electrode plate taken from the cell before and after 50 cycles. - In
FIG. 8 , a graph in red denotes when the first carbon coating layer was not formed (Graphite+Si+Carbon, Comparative Example 2), and a graph in orange denotes when the first carbon coating layer was formed (Example). - Referring to the table in
FIG. 8 , the final material including the first carbon coating layer (Graphite +Carbon +Si +Carbon, Example) were found to have improved volume expansions characteristics by about 20%, compared to that of Comparative Example 2. -
FIG. 9 shows evaluation data of rate characteristics. InFIG. 9 , "Graphite" denotes a sample of Comparative Example 1, "UNIST 600 class" denotes a sample of Example), "Lithiation" denotes high-rate charge characteristics at 0.5C, 1C. 2C, 3C, and 5C, and "De-lithiation" denotes high-rate discharge characteristics at 0.5C, 1C, 2C, 3C, and 5C. - In
FIG. 9 , the X-axis denotes the number of cycles, and the Y-axis denotes normalized capacity retention. - Graphite has a reversible capacity (i.e., non-theoretical actual capacity) of about 357mAh/g as a result of normalization. The material of Example was found to have a reversible capacity of about 600mAh/g. Based on these two initial reversible capacities (100%), a degree of capacity drop (%) with respect to the initial reversible capacity with increasing C-rates was evaluated. As a result, the cell of Example was found to have considerably improved battery characteristics.
- It should be understood that embodiments described herein should be considered in a descriptive sense only and not for purposes of limitation. Descriptions of features or aspects within each embodiment should typically be considered as available for other similar features or aspects in other embodiments.
- While one or more embodiments have been described with reference to the figures, it will be understood by those of ordinary skill in the art that various changes in form and details may be made therein without departing from the spirit and scope as defined by the following claims.
Claims (21)
- An anode active material for a lithium secondary battery, comprising:carbon particles having a spherical shape;a first carbon coating layer present on surfaces of the carbon particles;a silicon coating layer present on the first carbon coating layer and including silicon nanoparticles; anda second carbon coating layer present on the silicon coating layer.
- The anode active material of claim 1, wherein the carbon particles having the first carbon coating layer thereon have an about 10% or greater increased Brunauer-Emmett-Teller (BET) specific surface area with respect to a BET specific surface area of the carbon particles having the spherical shape.
- The anode active material of claim 1, wherein the carbon particles having the first carbon coating layer thereon have an about 10% or greater decreased Brunauer-Emmett-Teller (BET) specific surface area with respect to a BET specific surface area of the carbon particles having the spherical shape.
- The anode active material of claim 1, wherein the silicon nanoparticles are semicrystalline.
- The anode active material of claim 1, wherein the first carbon coating layer partially includes a mixed layer of silicon and carbon.
- The anode active material of claim 5, wherein the mixed layer of silicon and carbon layer has a concentration gradient in which an amount of silicon decreases in the direction of a core.
- The anode active material of claim 1, wherein the silicon coating layer present on the first carbon coating layer is in a mixed form of a film and an island.
- The anode active material of claim 1, wherein a content ratio of silicon to carbon is 3:97 to 20:80, with respect to a total weight of the anode active material.
- The anode active material of claim 1, wherein the anode active material includes 2wt% to 6wt% of the first carbon coating layer, 4wt% to 20wt% of the silicon coating layer, and 1.5wt% to 10wt% of the second carbon coating layer, each based on a total of 100wt% of the anode active material, and the remainder is the carbon particles.
- The anode active material of claim 1, wherein the carbon particles comprise graphite, amorphous carbon, or a combination thereof.
- The anode active material of claim 1, wherein the carbon particles have a particle diameter of 5 µm to 20 µm.
- The anode active material of claim 1, wherein the first carbon coating layer has a thickness of 5 nm to 200 nm.
- The anode active material of claim 1, wherein the silicon coating layer has a thickness of 20 nm to 60 nm.
- The anode active material of claim 1, wherein the second carbon coating layer has a thickness of 5 nm to 200 nm.
- A method of preparing an anode active material for a lithium secondary battery, the method comprising:preparing carbon particles having a spherical shape;forming a first carbon coating layer on surfaces of the carbon particles;forming, on the first carbon coating layer, a silicon coating layer including silicon nanoparticles; andforming a second carbon coating layer on the silicon coating layer.
- The method of claim 15, wherein the forming of the first carbon coating layer on the surfaces of the carbon particles is performed using a sol-gel method.
- The method of claim 15, wherein the forming of the first carbon coating layer on the surfaces of the carbon particles is performed using a chemical vapor deposition method.
- The method of claim 15, wherein, in the forming of the silicon coating layer including silicon nanoparticles on the first carbon coating layer, the silicon nanoparticles are amorphous.
- The method of claim 15, wherein, in the forming of the silicon coating layer including silicon nanoparticles on the first carbon coating layer, the silicon coating layer is deposited in a mixed form of a film and an island.
- The method of claim 15, wherein the forming of the second carbon coating layer on the silicon coating layer is performed using a physical milling method, a sol-gel method, or a chemical vapor deposition method.
- A lithium secondary battery comprising:a cathode;an anode; andan electrolyte,wherein the anode comprises the anode active material of claim 1.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
KR20150084157 | 2015-06-15 | ||
PCT/KR2016/006357 WO2016204512A1 (en) | 2015-06-15 | 2016-06-15 | Anode active material for lithium secondary battery, preparation method therefor, and lithium secondary battery containing same |
Publications (3)
Publication Number | Publication Date |
---|---|
EP3309873A1 true EP3309873A1 (en) | 2018-04-18 |
EP3309873A4 EP3309873A4 (en) | 2019-04-10 |
EP3309873B1 EP3309873B1 (en) | 2020-05-27 |
Family
ID=57546568
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP16811925.3A Active EP3309873B1 (en) | 2015-06-15 | 2016-06-15 | Anode active material for lithium secondary battery, preparation method therefor, and lithium secondary battery containing same |
Country Status (7)
Country | Link |
---|---|
US (1) | US10340518B2 (en) |
EP (1) | EP3309873B1 (en) |
JP (1) | JP6748120B2 (en) |
KR (1) | KR101933098B1 (en) |
CN (1) | CN107925064B (en) |
HU (1) | HUE051614T2 (en) |
WO (1) | WO2016204512A1 (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP3863088A4 (en) * | 2019-12-06 | 2022-07-06 | Livenergy Co., Ltd. | Electrode active material for secondary battery, electrode and secondary battery which comprise same, and method for preparing electrode active material |
Families Citing this family (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP3428999A1 (en) * | 2017-07-12 | 2019-01-16 | Evonik Degussa GmbH | Silicon-carbon composite powder |
KR101963164B1 (en) * | 2017-07-14 | 2019-03-28 | (주)에스제이신소재 | Negative active material for lithium secondary battery and manufacturing method thereof |
CN107834047B (en) * | 2017-11-10 | 2023-10-13 | 河南中联高科新能源有限公司 | Preparation method and device of silicon-carbon anode material |
US10468674B2 (en) * | 2018-01-09 | 2019-11-05 | South Dakota Board Of Regents | Layered high capacity electrodes |
KR102131262B1 (en) * | 2018-08-14 | 2020-08-05 | 울산과학기술원 | an anode active material, a method of preparing the anode active material, and Lithium secondary battery comprising an anode including the anode active material |
KR102179975B1 (en) * | 2018-11-30 | 2020-11-17 | 주식회사 포스코 | Negative electrode active material for rechargeable lithium battery, method for manufacturing of the same, and rechargeable lithium battery including the same |
KR102323509B1 (en) * | 2018-12-21 | 2021-11-09 | 울산과학기술원 | Composite anode active material, a method of preparing the composite anode material, and a lithium secondary battery comprising the composite anode active material |
WO2020235748A1 (en) * | 2019-05-17 | 2020-11-26 | 주식회사 엘아이비에너지 | Silicon-graphite composite electrode active material for lithium secondary battery, electrode and lithium secondary battery which comprise same, and method for preparing silicon-graphite composite electrode active material |
KR102380024B1 (en) * | 2019-06-21 | 2022-03-29 | 삼성에스디아이 주식회사 | A composite anode, and lithium secondary battery comprising the anode |
CN112678801B (en) * | 2019-10-17 | 2022-06-21 | 拓米(成都)应用技术研究院有限公司 | Nano amorphous C-Si-C composite material and manufacturing method and manufacturing device thereof |
CN110931725B (en) * | 2019-10-21 | 2021-06-04 | 浙江工业大学 | Silicon-carbon composite material and preparation method and application thereof |
CN111682186B (en) * | 2020-06-28 | 2021-09-17 | 蜂巢能源科技有限公司 | Silicon-carbon composite material, preparation method and application thereof |
KR102221105B1 (en) * | 2020-09-02 | 2021-02-26 | 주식회사 유로셀 | Method for manufacturing silicon graphite composite anode material for secondary battery |
CN114335533A (en) * | 2021-12-16 | 2022-04-12 | 珠海冠宇电池股份有限公司 | Negative electrode material and battery comprising same |
WO2023240381A1 (en) * | 2022-06-13 | 2023-12-21 | 宁德时代新能源科技股份有限公司 | Negative electrode active material and preparation method therefor, secondary battery, and electric apparatus |
Family Cites Families (22)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP3685364B2 (en) * | 1999-03-23 | 2005-08-17 | シャープ株式会社 | Method for producing carbon-coated graphite particles and non-aqueous secondary battery |
KR100529069B1 (en) | 1999-12-08 | 2005-11-16 | 삼성에스디아이 주식회사 | Negative active material for lithium secondary battery and method of preparing same |
JP4137350B2 (en) * | 2000-06-16 | 2008-08-20 | 三星エスディアイ株式会社 | Negative electrode material for lithium secondary battery, electrode for lithium secondary battery, lithium secondary battery, and method for producing negative electrode material for lithium secondary battery |
US6733922B2 (en) * | 2001-03-02 | 2004-05-11 | Samsung Sdi Co., Ltd. | Carbonaceous material and lithium secondary batteries comprising same |
JP2004185975A (en) * | 2002-12-03 | 2004-07-02 | Samsung Yokohama Research Institute Co Ltd | Compound carbon material for lithium ion secondary battery negative electrode and its manufacturing method |
US7618678B2 (en) * | 2003-12-19 | 2009-11-17 | Conocophillips Company | Carbon-coated silicon particle powders as the anode material for lithium ion batteries and the method of making the same |
KR100738054B1 (en) | 2004-12-18 | 2007-07-12 | 삼성에스디아이 주식회사 | Anode active material, method of preparing the same, and anode and lithium battery containing the material |
DE102005011940A1 (en) | 2005-03-14 | 2006-09-21 | Degussa Ag | Process for the preparation of coated carbon particles and their use in anode materials for lithium-ion batteries |
US8329136B2 (en) | 2005-12-14 | 2012-12-11 | Nippon Coke & Engineering Company, Limited | Graphite particle, carbon-graphite composite particle and their production processes |
JP4986222B2 (en) * | 2006-01-31 | 2012-07-25 | Jfeケミカル株式会社 | Method for producing negative electrode material for lithium ion secondary battery |
JP2007311180A (en) * | 2006-05-18 | 2007-11-29 | Teijin Ltd | Negative electrode for lithium secondary battery, and its manufacturing method |
JP5143437B2 (en) * | 2007-01-30 | 2013-02-13 | 日本カーボン株式会社 | Method for producing negative electrode active material for lithium ion secondary battery, negative electrode active material, and negative electrode |
KR101075028B1 (en) * | 2008-04-24 | 2011-10-20 | 쇼와 덴코 가부시키가이샤 | Carbon anode material for lithium secondary battery, method for preparing the same, and lithium secondary battery using the same |
JP5682276B2 (en) * | 2010-12-10 | 2015-03-11 | 日立化成株式会社 | Negative electrode material for lithium ion secondary battery and method for producing the same, negative electrode for lithium ion secondary battery, and lithium ion secondary battery |
KR101142534B1 (en) * | 2011-06-02 | 2012-05-07 | 한국전기연구원 | Process for producing si-based nanocomposite anode material for lithium secondary battery and lithium secondary battery including the same |
WO2013125710A1 (en) * | 2012-02-24 | 2013-08-29 | 三菱化学株式会社 | Multilayer-structure carbon material for nonaqueous secondary batteries, negative electrode for nonaqueous secondary batteries using same, and nonaqueous secondary battery |
JP2013222641A (en) * | 2012-04-18 | 2013-10-28 | Showa Denko Kk | Negative electrode material for lithium ion battery and application thereof |
WO2013183187A1 (en) * | 2012-06-06 | 2013-12-12 | 日本電気株式会社 | Negative electrode active material and manufacturing process therefor |
WO2014080629A1 (en) * | 2012-11-20 | 2014-05-30 | 昭和電工株式会社 | Method for producing negative electrode material for lithium ion batteries |
KR101557559B1 (en) * | 2012-11-30 | 2015-10-07 | 주식회사 엘지화학 | Anode active material for lithium secondary battery, preparation method thereof, and lithium secondary battery comprising the same |
US9711787B2 (en) | 2012-11-30 | 2017-07-18 | Lg Chem, Ltd. | Anode active material for lithium secondary battery, preparation method thereof, and lithium secondary battery comprising the same |
KR101698763B1 (en) * | 2012-12-10 | 2017-01-23 | 삼성에스디아이 주식회사 | Anode electrode material, preparation method thereof, electrode comprising the material, and lithium secondary battery comprising the electrode |
-
2016
- 2016-06-15 JP JP2017565264A patent/JP6748120B2/en active Active
- 2016-06-15 CN CN201680048132.9A patent/CN107925064B/en active Active
- 2016-06-15 EP EP16811925.3A patent/EP3309873B1/en active Active
- 2016-06-15 US US15/737,040 patent/US10340518B2/en active Active
- 2016-06-15 WO PCT/KR2016/006357 patent/WO2016204512A1/en active Application Filing
- 2016-06-15 HU HUE16811925A patent/HUE051614T2/en unknown
- 2016-06-15 KR KR1020160074481A patent/KR101933098B1/en active IP Right Grant
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP3863088A4 (en) * | 2019-12-06 | 2022-07-06 | Livenergy Co., Ltd. | Electrode active material for secondary battery, electrode and secondary battery which comprise same, and method for preparing electrode active material |
Also Published As
Publication number | Publication date |
---|---|
WO2016204512A1 (en) | 2016-12-22 |
US10340518B2 (en) | 2019-07-02 |
CN107925064B (en) | 2021-03-19 |
JP6748120B2 (en) | 2020-08-26 |
EP3309873A4 (en) | 2019-04-10 |
KR101933098B1 (en) | 2018-12-27 |
KR20160147672A (en) | 2016-12-23 |
HUE051614T2 (en) | 2021-03-01 |
US20180337400A1 (en) | 2018-11-22 |
EP3309873B1 (en) | 2020-05-27 |
CN107925064A (en) | 2018-04-17 |
JP2018524774A (en) | 2018-08-30 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP3309873B1 (en) | Anode active material for lithium secondary battery, preparation method therefor, and lithium secondary battery containing same | |
KR20210107063A (en) | Electroactive materials for metal-ion batteries | |
KR102063809B1 (en) | Negative active material for lithium secondary battery, method of manufacturing the same, and lithium secondary battery including the same | |
KR102576471B1 (en) | Cathode and Cathode Materials for Lithium Sulfur Batteries | |
KR102632717B1 (en) | Electroactive materials for metal-ion batteries | |
JP6517326B2 (en) | Method of manufacturing negative electrode active material for lithium secondary battery | |
KR101665099B1 (en) | Anode materials for lithium rechargeable batteries including natural graphite and metal and a preparation method thereof | |
KR101929413B1 (en) | Negative active material for lithium secondary battery, method of manufacturing the same, and lithium secondary battery including the same | |
EP4160728A1 (en) | Negative electrode material for lithium ion secondary battery, and use thereof | |
KR20180072112A (en) | Negative active material for lithium secondary battery, method of manufacturing the same, and lithium secondary battery including the same | |
US20240047678A1 (en) | Negative electrode active material for lithium secondary battery, method for manufacturing the same, and lithium secondary battery comprising the same | |
EP3994745A1 (en) | Electroactive materials for metal-ion batteries | |
KR102635072B1 (en) | Negative active material for lithium secondary battery, method of manufacturing the same, and lithium secondary battery including the same | |
KR20220065124A (en) | Anode active material including core-shell composite and method for manufacturing same | |
WO2021241750A1 (en) | Composite particles, negative electrode material, and lithium ion secondary battery | |
KR102286235B1 (en) | Lithium doped silicon oxide negative active material, method of preparing the same, negative electrode including the same and lithium secondary battery including the same | |
KR102286227B1 (en) | Lithium doped silicon oxide negative active material, method of preparing the same, negative electrode including the same and lithium secondary battery including the same | |
Kim et al. | Viable post-electrode-engineering for the complete integrity of large-volume-change lithium-ion battery anodes | |
KR102013826B1 (en) | Negative active material for lithium secondary battery, and lithium secondary battery including the same | |
WO2022270539A1 (en) | Composite carbon particles and use thereof |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: THE INTERNATIONAL PUBLICATION HAS BEEN MADE |
|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE |
|
17P | Request for examination filed |
Effective date: 20180115 |
|
AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR |
|
AX | Request for extension of the european patent |
Extension state: BA ME |
|
DAV | Request for validation of the european patent (deleted) | ||
DAX | Request for extension of the european patent (deleted) | ||
A4 | Supplementary search report drawn up and despatched |
Effective date: 20190313 |
|
RIC1 | Information provided on ipc code assigned before grant |
Ipc: H01M 10/0525 20100101ALI20190306BHEP Ipc: H01M 10/052 20100101ALI20190306BHEP Ipc: H01M 4/02 20060101ALI20190306BHEP Ipc: H01M 4/38 20060101ALI20190306BHEP Ipc: H01M 4/36 20060101AFI20190306BHEP Ipc: C01B 33/029 20060101ALI20190306BHEP Ipc: H01M 4/62 20060101ALI20190306BHEP Ipc: H01M 4/587 20100101ALI20190306BHEP |
|
GRAP | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOSNIGR1 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: GRANT OF PATENT IS INTENDED |
|
INTG | Intention to grant announced |
Effective date: 20191213 |
|
RIN1 | Information on inventor provided before grant (corrected) |
Inventor name: MA, JI YOUNG Inventor name: KIM, NAM HYUNG Inventor name: CHAE, SUJONG Inventor name: CHO, JAEPHIL Inventor name: KO, MIN SEONG |
|
GRAS | Grant fee paid |
Free format text: ORIGINAL CODE: EPIDOSNIGR3 |
|
GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: THE PATENT HAS BEEN GRANTED |
|
AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR |
|
REG | Reference to a national code |
Ref country code: GB Ref legal event code: FG4D |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: EP |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R096 Ref document number: 602016037170 Country of ref document: DE |
|
REG | Reference to a national code |
Ref country code: AT Ref legal event code: REF Ref document number: 1275499 Country of ref document: AT Kind code of ref document: T Effective date: 20200615 |
|
REG | Reference to a national code |
Ref country code: LT Ref legal event code: MG4D |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SE Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20200527 Ref country code: LT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20200527 Ref country code: NO Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20200827 Ref country code: GR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20200828 Ref country code: PT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20200928 Ref country code: IS Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20200927 Ref country code: FI Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20200527 |
|
REG | Reference to a national code |
Ref country code: NL Ref legal event code: MP Effective date: 20200527 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: LV Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20200527 Ref country code: RS Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20200527 Ref country code: HR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20200527 Ref country code: BG Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20200827 |
|
REG | Reference to a national code |
Ref country code: AT Ref legal event code: MK05 Ref document number: 1275499 Country of ref document: AT Kind code of ref document: T Effective date: 20200527 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: NL Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20200527 Ref country code: AL Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20200527 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: RO Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20200527 Ref country code: IT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20200527 Ref country code: CZ Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20200527 Ref country code: DK Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20200527 Ref country code: AT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20200527 Ref country code: ES Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20200527 Ref country code: SM Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20200527 Ref country code: EE Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20200527 |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: PL |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SK Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20200527 Ref country code: PL Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20200527 Ref country code: MC Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20200527 |
|
REG | Reference to a national code |
Ref country code: HU Ref legal event code: AG4A Ref document number: E051614 Country of ref document: HU |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R097 Ref document number: 602016037170 Country of ref document: DE |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R082 Ref document number: 602016037170 Country of ref document: DE Representative=s name: HOFFMANN - EITLE PATENT- UND RECHTSANWAELTE PA, DE Ref country code: DE Ref legal event code: R081 Ref document number: 602016037170 Country of ref document: DE Owner name: SJ ADVANCED MATERIALS CO., LTD., KR Free format text: FORMER OWNER: UNIST (ULSAN NATIONAL INSTITUTE OF SCIENCE AND TECHNOLOGY), ULSAN, KR |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: LU Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20200615 |
|
PLBE | No opposition filed within time limit |
Free format text: ORIGINAL CODE: 0009261 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT |
|
RAP2 | Party data changed (patent owner data changed or rights of a patent transferred) |
Owner name: SJ ADVANCED MATERIALS CO., LTD. |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: IE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20200615 Ref country code: CH Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20200630 Ref country code: LI Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20200630 |
|
26N | No opposition filed |
Effective date: 20210302 |
|
REG | Reference to a national code |
Ref country code: BE Ref legal event code: PD Owner name: SJ ADVANCED MATERIALS CO., LTD; KR Free format text: DETAILS ASSIGNMENT: CHANGE OF OWNER(S), ASSIGNMENT; FORMER OWNER NAME: UNIST (ULSAN NATIONAL INSTITUTE OF SCIENCE AND TECHNOLOGY) Effective date: 20210331 |
|
REG | Reference to a national code |
Ref country code: HU Ref legal event code: GB9C Owner name: SJ ADVANCED MATERIALS CO., LTD., KR Free format text: FORMER OWNER(S): UNIST (ULSAN NATIONAL INSTITUTE OF SCIENCE AND TECHNOLOGY), KR |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SI Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20200527 |
|
REG | Reference to a national code |
Ref country code: GB Ref legal event code: 732E Free format text: REGISTERED BETWEEN 20210603 AND 20210609 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: TR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20200527 Ref country code: MT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20200527 Ref country code: CY Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20200527 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: MK Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20200527 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: FR Payment date: 20230321 Year of fee payment: 8 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: BE Payment date: 20230321 Year of fee payment: 8 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: DE Payment date: 20230320 Year of fee payment: 8 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: HU Payment date: 20230421 Year of fee payment: 8 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: GB Payment date: 20230405 Year of fee payment: 8 |